Kinetics Modeling of Glycerol Carbonate Synthesis from Glycerol and Urea over Amberlyst-15 Catalyst

https://doi.org/10.22146/ijc.42879

Hary Sulistyo(1*), Sabariyanto Sabariyanto(2), Muhammad Noor Ridho Aji(3), Muhammad Mufti Azis(4)

(1) Department of Chemical Engineering, Universitas Gadjah Mada, Jl. Grafika No 2, Yogyakarta 55281, Indonesia
(2) Department of Chemical Engineering, Universitas Gadjah Mada, Jl. Grafika No 2, Yogyakarta 55281, Indonesia
(3) Department of Chemical Engineering, Universitas Gadjah Mada, Jl. Grafika No 2, Yogyakarta 55281, Indonesia
(4) Department of Chemical Engineering, Universitas Gadjah Mada, Jl. Grafika No 2, Yogyakarta 55281, Indonesia
(*) Corresponding Author

Abstract


Synthesize of glycerol carbonate from glycerol and urea is an attractive path as glycerol carbonate has a large potential as a green solvent. The aim of the present study was to develop a kinetic model of glycerol carbonate synthesis with amberlyst-15 resins as a catalyst. The investigation was carried out at various temperatures from 353 to 383 K and catalyst loading from 0.25 to 1 wt.% of glycerol. The experimental results indicated that both temperature and catalyst loading have an important effect on the glycerol conversion. According to the experimental result, the highest glycerol conversion was found 36.90% which was obtained using a molar ratio of urea to glycerol 1:3, catalyst loading of 1 wt.%, stirrer speed of 700 rpm, the temperature of 383 K and reaction time of 5 h. A kinetic model was developed based on elementary steps that take place over the catalyst. The model estimated that the pre-exponential factor was 2.89.104 mol.g–1.min–1 and the activation energy was 50.5 kJ.mol–1. By comparing the simulation and experimental data, it could be inferred that the model could predict the trend of experimental data well over the range of temperature and catalyst loading investigated in the present study.

Keywords


amberlyst-15; glycerolysis; glycerol carbonate; kinetic modeling

Full Text:

Full Text PDF


References

[1] Peraturan Presiden Republik Indonesia No. 22, 2017, Rencana umum energi nasional, Sekretariat Kabinet Republik Indonesia.

[2] Peraturan Presiden Republik Indonesia No. 66, 2018, Perubahan kedua atas peraturan presiden nomor 61 tahun 2015 tentang penghimpunan dan penggunaan dana perkebunan kelapa sawit, Sekretariat Kabinet Republik Indonesia.

[3] Aresta, M., Dibenedetto, A., Nocito, F., and Ferragina, C., 2009, Valorization of bio-glycerol: New catalytic materials for the synthesis of glycerol carbonate via glycerolysis of urea, J. Catal., 268 (1), 106–114.

[4] Climent, M.J., Corma, A., De Frutos, P., Iborra, S., Noy, M., Velty, A., and Concepción, P., 2010, Chemicals from biomass: Synthesis of glycerol carbonate by transesterification and carbonylation with urea with hydrotalcite catalysts. The role of acid-base pairs, J. Catal., 269 (1), 140–149.

[5] Fernandes, G.P., and Yadav, G.D., 2018, Selective glycerolysis of urea to glycerol carbonate using combustion synthesized magnesium oxide as catalyst, Catal. Today, 309, 153–160.

[6] Hammond, C., Lopez-Sanchez, J.A., Ab Rahim, M.H., Dimitratos, N., Jenkins, R.L., Carley, A.F., He, Q., Kiely, C.J., Knight, D.W., and Hutchings, G.J., 2011, Synthesis of glycerol carbonate from glycerol and urea with gold-based catalysts, Dalton Trans., 40 (15), 3927–3937.

[7] Kim, D.W., Kim, M.J., Roshith, K., Kim, M.I., Kwak, J.Y., and Park, D.W., 2014, Comparative catalytic activity of supported ZnBr2-containing ionic liquid catalysts for the preparation of glycerol carbonate by glycerolysis of urea, Korean J. Chem. Eng., 31 (6), 972–980.

[8] Lee, S.D., Park, M.S., Kim, D.W., Kim, I., and Park, D.W., 2014, Catalytic performance of ion-exchanged montmorillonite with quaternary ammonium salts for the glycerolysis of urea, Catal. Today, 232, 127–133.

[9] Nguyen-Phu, H., and Shin, E.W., 2018, Investigating time-dependent Zn species over Zn-based catalysts in glycerol carbonylation with urea and their roles in the reaction mechanism, Appl. Catal., A, 561, 28–40.

[10] Park, J.H., Choi, J.S., Woo, S.K., Lee, S.D., Cheong, M., Kim, H.S., and Lee, H., 2012, Isolation and characterization of intermediate catalytic species in the Zn-catalyzed glycerolysis of urea, Appl. Catal., A, 433-434, 35–40.

[11] Singh, D., Reddy, B., Ganesh, A., and Mahajani, S., 2014, Zinc/lanthanum mixed-oxide catalyst for the synthesis of glycerol carbonate by transesterification of glycerol, Ind. Eng. Chem. Res., 53 (49), 18786–18795.

[12] Wang, D., Zhang, X., Cong, X., Liu, S., and Zhou, D., 2018, Influence of Zr on the performance of Mg-Al catalysts via hydrotalcite-like precursors for the synthesis of glycerol carbonate from urea and glycerol, Appl. Catal., A, 555, 36–46.

[13] Endah, Y.K., Kim, M.S., Choi, J., Jae, J., Lee, S.D., and Lee, H., 2017, Consecutive carbonylation and decarboxylation of glycerol with urea for the synthesis of glycidol via glycerol carbonate, Catal. Today, 293-294, 136–141.

[14] Granados-Reyes, J., Salagre, P., and Cesteros, Y., 2018, Boosted selectivity towards glycerol carbonate using microwaves vs conventional heating for the catalytic transesterification of glycerol, Appl. Clay Sci., 156, 110–115.

[15] Lertlukkanasuk, N., Phiyanalinmat, S., Kiatkittipong, W., Arpornwichanop, A., Aiouache, F., and Assabumrungrat, S., 2013, Reactive distillation for synthesis of glycerol carbonate via glycerolysis of urea, Chem. Eng. Process. Process Intensif., 70, 103–109.

[16] Esteban, J., Domínguez, E., Ladero, M., and Garcia-Ochoa, F. 2015, Kinetics of the production of glycerol carbonate by transesterification of glycerol with dimethyl and ethylene carbonate using potassium methoxide, a highly active catalyst, Fuel Process. Technol., 138, 243–251.

[17] Sabariyanto and Aji, M.N.R, 2017, Pengaruh suhu reaksi terhadap sintesis gliserol karbonat dari gliserol dan urea menggunakan katalis amberlyst-15TM, Laporan Penelitian Laboratorium Teknik Reaksi Kimia dan Katalisis, Department of Chemical Engineering, Universitas Gadjah Mada, Yogyakarta.

[18] Li, J., and Wang, T., 2011, Chemical equilibrium of glycerol carbonate synthesis from glycerol, J. Chem. Thermodyn., 43 (5), 731–736.

[19] Sulistyo, H., Sediawan, W.B., and Rahayu, S.S., 2016, Utilization of glycerol with urea using purolite C100 resin as catalyst, The 23rd Regional Symposium on Chemical Engineering –RSCE 2016, 27–28 October 2016, Vung Tau, Vietnam.

[20] Kondawar, S.E., Mane, R.B., Vasishta, A., More, S.B., Dhengale, S.D., and Rode, C.V., 2017, Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts, Appl. Petrochem. Res., 7 (1), 41–53.

[21] Bartoli, M., Zhu, C., Chae, M., and Bressler, D.C., 2018, Value-added products from urea glycerolysis using a heterogeneous biosolids-based catalyst, Catalysts, 8, 373.



DOI: https://doi.org/10.22146/ijc.42879

Article Metrics

Abstract views : 3489 | views : 3050


Copyright (c) 2019 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

 


Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Web
Analytics View The Statistics of Indones. J. Chem.